Hydrophobic TiO2/SiO2 (TiO2/HSiO2) membrane was fabricated by sol-gel method using methyltriethoxysilane as a precursor instead of partial tetraethylorthosilicate. The thermal stability of the composites was characterized by Fourier transform infrared spectra, X-ray diffraction, thermogravimetric-differential thermogravimetric analysis and N2 adsorption-desorption measurements. The H2 permeation and H2 permselectivity of TiO2/HSiO2 membrane were investigated by single gas permeance test. Calcination at about 350 ∼ 400 °C is suitable for preserving the hydrophobicity of the TiO2/HSiO2 membrane. The H2 permeance and H2 permselectivity in TiO2/HSiO2 membranes increased significantly with growing temperatures. At 200 °C and 0.4 MPa, the H2 permeance of TiO2/HSiO2 membrane is 7.27 × 10−6 mol·m−2·Pa−1·s−1 and the H2/CO2 and H2/N2 permselectivities are 7.68 and 10.09, respectively. In comparison to the HSiO2 membrane, the H2 permeances of TiO2/HSiO2 membrane increased by 71.56%, and the H2/CO2 and H2/N2 permselectivities increased by 23.07% and 24.11%, respectively. After steam treatment, the water absorption rate of TiO2/HSiO2 materials decreased by 33.17% relative to that of HSiO2 materials. TiO2/HSiO2 membrane has better hydrothermal stability and reproducibility than HSiO2 membrane.